Titanium-based Catalysts Research Articles

Engineering of a wafer-shaped titanium-based catalyst of TiO2/MIL-125(Ti)@Ti3C2 for enhanced Fenton-like degradation of Congo red: Optimization, mechanistic study, and reusability

A titanium-based Fenton-like heterogeneous catalyst was synthesized from titanium dioxide (TiO2), MIL-125(Ti), and Ti3C2 MXene for degrading the notorious Congo red (CR). The successful combination of the titanium components was assured by bountiful characterization apparatuses. Optimization of the conditions for the Fenton-like degradation of CR dye was performed by studying the impact of the pH and temperature of the catalytic system, the dosage of TiO2/MIL-125(Ti)@Ti3C2, the concentrations of hydrogen peroxide (H2O2) and CR, and the mass ratio between the catalyst’s components. A kinetic study was executed on the degradation of CR and H2O2 during a reaction time of 60 min using First-order and Second-order models. The degradation pathway of CR by TiO2/MIL-125(Ti)@Ti3C2 was investigated by the scavenging test. Additionally, Adsorption and catalytic degradation mechanisms were explored using X-Ray Photoelectron Spectroscopy (XPS) analysis. The cycling test proceeded on TiO2/MIL-125(Ti)@Ti3C2 for five succeeding Fenton-like degradation runs of CR dye. Ultimately, the Ti-based heterogeneous catalyst exhibited superior adsorption and Fenton-like degradation performance toward the anionic dye with a good recyclability feature.

Accelerating Toluene Oxidation over Boron-Titanium-Oxygen Interface: Steric Hindrance of the Methyl Group Induced by the Plane-Adsorption Configuration.

Elimination of dilute gaseous toluene is one of the critical concerns within the field of indoor air remediation. The typical degradation route on titanium-based catalysts, "toluene-benzaldehyde-carbon dioxide", necessitates the oxidation of the methyl group as a prerequisite for photocatalytic toluene oxidation. However, the inherent planar adsorption configuration of toluene molecules, dominated by the benzene rings, leads to significant steric hindrance for the methyl group. This steric hindrance prevents the methyl group from contacting the active species on the catalyst surface, thereby limiting the removal of toluene under indoor conditions. To date, no effective strategy to control the steric hindrance of the methyl group has been identified. Herein, we showed a B-Ti-O interface that exhibits significantly enhanced toluene removal efficiency under indoor conditions. In-depth investigations revealed that, compared to typical Ti-based photocatalysts, the steric hindrance between the methyl group and the catalyst surface decreased from 3.42 to 3.03 Å on the designed interface. This reduction originates from the matching of orbital energy levels between Ti 3dz2 and C 2pz of the benzene ring. The decreased steric hindrance improved the efficiency of toluene being attacked by surface active species, allowing for rapid conversion into benzaldehyde and benzoic acid species for subsequent reactions. Our work provides novel insights into the steric hindrance effect in the elimination of aromatic volatile organic compounds.

Titanium-Immobilized Layered HUS-7 Silicate as a Catalyst for Photocatalytic CO2 Reduction.

Utilizing photocatalytic CO2 reduction presents a promising avenue for combating climate change and curbing greenhouse gas emissions. However, maximizing its potential hinges on the development of materials that not only enhance efficiency but also ensure process stability. Here, we introduce Hiroshima University Silicate-7 (HUS-7) with immobilized Ti species as a standout contender. Our study demonstrates the remarkable photocatalytic activity of HUS-7 in CO2 reduction, yielding substantially higher carbonaceous product yields compared to conventional titanium-based catalysts TS-1 and P25. Through thorough characterization, we elucidate that their boosted photocatalytic performance is attributed to the incorporation of isolated Ti species within the silica-based precursor, serving as potent photoinduced active sites. Moreover, our findings underscore the crucial role of the Ligand-to-Metal Charge Transfer (LMCT) process in facilitating the photoactivation of CO2 molecules, shedding new light on key mechanisms underlying photocatalytic CO2 reduction.

Recent Advances in the Titanium-Based Catalysts for Ring-Opening Polymerization.

At present, economic development and daily life cannot be separated from organic synthetic polymers. However, a large number of nondegradable polymers have caused serious pollution to the environment. It is necessary for sustainable development to use biodegradable materials instead of traditional polymers, but it is not yet comparable in performance and cost to the competitor it will replace. Therefore, there is a long way to go to develop effective synthesis methods. Through ring-opening polymerization, some cyclic monomers, such as ε-caprolactone or lactide, can be synthesized into biodegradable polymers, which can not only replace traditional synthetic polymers in some fields but also have applications in drug delivery, surgical consumables, human implant materials, bone materials, etc. Ring-opening polymerization is a potential candidate for solving environmental pollution. For ring-opening polymerization, catalysts are very important, among which titanium catalysts have attracted much attention because of their high efficiency, economy, and nontoxicity. In this paper, the development status of organotitanium compounds as ring-opening polymerization catalysts is reviewed, including the effects of different ligand structures on polymerization behavior and polymer structure, and its development trend is prospected. We hope that this review will be helpful for developing efficient ring-opening polymerization catalysts.

In situ EPR spin-trapping tracking of macroradical formation and the role of a hindered phenol anti-oxidant in reducing thermo-oxidative phenomena of poly(ethylene terephthalate)

One of the major issues concerning poly(ethylene terephthalate) (PET) produced with titanium-based catalysts is its sensitivity to high-temperature oxidation, which results in performance loss and discoloration. Here, the thermo-oxidative phenomena of titanium-catalyst-produced PET during its synthesis and post-processing in the presence of hindered phenol anti-oxidant Irganox 1425 has been investigated by a spin-trapping technique. Three types of spin adducts have been determined and quantified; –O−•CH− is the dominant radical intermediate, while •CH2− and –O−•CH− are mainly produced by the decomposition of diethylene glycol (DEG) units. An excessively high DEG content leads to instability of PET chains at high temperatures and so is not conducive to suppressing oxidation. An anti-oxidant can effectively eliminate radicals induced by thermo-oxidative reactions and improve the thermal stability of PET, especially in the post-processing stage. A comprehensive thermal oxidation mechanism is proposed, in which PET thermolysis starts with hydrogen abstraction to produce –O−•CH−, and then auto-oxidation ensues by radical intermediates attacking other PET chains. The cyclic reaction is reasonably terminated by the anti-oxidant serving as a hydrogen donor to quench radical intermediates.

Insights into the role of S-Ti-O bond in Titanium-Based catalyst for photocatalytic CH4 reforming: Experimental and DFT exploration

Given the increasingly severe climate and energy crises, this paper proposes the concept of “room-temperature solar-powered CH4 reforming”, intended to achieve carbon emission reduction and efficiently use carbon-containing resources. However, traditional semiconductors as catalysts have some problems, such as few catalytic active sites and fast recombination of photogenerated electrons and holes, resulting in low efficiency of photocatalytic CH4 reforming. For this reason, a series of doped catalysts X-TiO2 (X = Br, N, and S) are prepared by introducing nonmetallic elements into the TiO2 lattice to construct oxygen defects. Notably, the CO yield of the S-TiO2 catalyst was 1048μ mol g−1, 65 times higher than the catalytic performance of bulk TiO2. Based on the functional density theory (DFT) calculation, the interaction between the S active site and the performance of photocatalytic CH4 reforming with oxygen defects is discussed in detail. The synergistic effect of the S site and the oxygen defect has been shown to rapidly activate C = O and C-H bonds at room temperature. Finally, based on the tracer experiment and DFT calculation, a possible mechanism of photocatalytic CH4 reforming at room temperature is proposed. This work provides a new research direction for achieving carbon neutrality at room temperature and a feasible technical scheme for the large-scale application of photocatalysts.

Titanium-Catalyzed Selective N-Alkylation of Amines with Alcohols via Borrowing Hydrogen Methodology.

The N-alkylation of amines with alcohols using earth-abundant and nonprecious metal catalysts has gained considerable attention in the pharmaceutical industry. We described titanium-catalyzed synthetic protocol for N-alkylation of amines with alcohols via borrowing hydrogen or hydrogen autotransfer reactions. The methodology enables the selective monoalkylation of various substituted (hetero)aromatic amines in good to excellent yields (up to 97% yield). The importance of the protocol was further demonstrated by the applicability of earth-abundant metal catalysis and the synthesis of 32 N-alkylated amines. The work allows the utilization of titanium-based catalysts for various reactions to expand the nature blueprint in catalysis.

Novel cerium–tungsten–titanium-based catalyst for an efficient oxidative desulfurization material in fuel oil under a laboratory-scale setup

Novel cerium–tungsten–titanium-based catalyst for an efficient oxidative desulfurization material in fuel oil under a laboratory-scale setup

Applicability of Titanium-Based Catalysts in the Photocatalytic Degradation of 2,3,7,8-Tetrachlorodibenzofuran.

Polychlorinated dibenzofurans (PCDFs) are persistent toxic compounds that are ubiquitous in the environment. Nanocomposites of titanium(IV) oxide-vanadium(III) oxide (Ti3V2O7) and titanium(IV) oxide-silicon dioxide (Ti2Si7O30) were prepared and spectroscopically analyzed as potential decontaminants for dioxin-like materials. The analysis confirmed a homogeneous morphology with nanoscale particle size. The Ti-Si sample was found to have a high surface area compared to the Ti-V composite. Vanadium(III) oxide (V2O5) and silicon dioxide (SiO2) were chosen as materials for the formation of heterogeneous compounds with titanium(IV) oxide (TiO2) because they possess a suitable band alignment with TiO2, thus forming effective photocatalysts. This study evaluated the photodegradation of 2,3,7,8-tetrachlorodibenzo-furan (TCDF) in the presence of Ti-Si and Ti-V oxide composites, which was tested using high- (254 nm) and midenergy (302 nm) UV irradiation sources. While Ti-Si showed success in the photodegradation of 2,3,7,8-TCDF dissolved in a (1:1) methanol-tetrahydrofuran (MeOH-THF) solution, the Ti-V composite proved to be a powerful material in adsorbing TCDF with a high capacity immediately upon mixing. Ti-Si oxide was found to decompose TCDF under the two irradiation sources with 98-99% degradation occurring after 70 min. The use of 254 nm as an irradiation source in the presence of Ti-Si was 4.3 times faster than the analogue reaction irradiated without a catalyst. Byproducts of the degradation were evaluated using gas chromatography-mass spectrometry (GC-MS), resulting in a lower chlorinated congener and less toxicity, as the main degradation product.

Developments in Titanium-Based Alkali and Alkaline Earth Metal Oxide Catalysts for Sustainable Biodiesel Production: A Review.

Biodiesel represents a biodegradable, environmentally friendly, and renewable alternative to fossil fuels. Despite more than three decades of research, significant obstacles still hinder the widespread production of biodiesel. This current review elucidates both the potential and the existing challenges associated with homogeneous and heterogeneous catalysts in catalyzing biodiesel production, with a particular focus on alkali analogues, alkaline earth metal oxides, and titania-based catalysts. In particular, a comprehensive analysis is presented concerning alkali and alkaline earth-based titania (TiO2 ) catalysts. Among these, the alkaline earth metal oxides, including lithium, calcium, and strontium when combined with titanium-based catalysts, exhibit superior catalytic activity compared to other metal oxides, owing to their heightened basicity. Consequently, this review offers a thorough and up-to-date insight into the potential of titania-based heterogeneous catalysts for advancing biodiesel production.

Performance of Titanium-Based Catalysts Loaded with Transition Metals (Cu, Mn and Fe) for Simultaneous Elimination of NO and Typical VOCs

Performance of Titanium-Based Catalysts Loaded with Transition Metals (Cu, Mn and Fe) for Simultaneous Elimination of NO and Typical VOCs

Novel resource utilization approach of spent catalyst from flue gas denitrification: Preparing high quality titanium-bearing pellets

Spent titanium-based catalyst is a waste generated by the selective catalytic reduction (SCR) denitrification process, whose generation is dramatically increasing in the iron and steel industry year by year. A novel approach was proposed in this work to prepare titanium-bearing pellets by using spent catalyst. The influences of spent catalyst addition on the comprehensive properties of pellets were studied. The corresponding relationship between the change of phase structure and the spent catalyst pellets' strength was investigated. The results demonstrated that the spent catalyst could be adsorbed on the surface of ore particles physically and chemically, improving the adhesion of particles inside the pellet and the hydrophilicity, thus obtaining good comprehensive performance of the green pellets. When adding 5.0 wt% spent catalyst, the bentonite dosage could be reduced by 50%, and the strength of roasted pellets could meet the requirement of large blast furnaces. The consolidation mechanism of the spent catalyst pellets indicated that TiO2 reacted with FeO first to generate FeTiO3 in the preheating process and further oxidized to form Fe2TiO5 in the roasting process. The unreacted TiO2 would appear in the roasted pellets and inhibit recrystallization and polycrystalline growth of Fe2O3 grains, resulting in the reduction of compressive strength. Overall, high-quality titanium-bearing pellets could be obtained when the amount of spent catalyst was less than 5.0 wt%. This study thus provided an alternative route to resource utilization of spent catalysts in iron and steel enterprises.

UiO-66(Zr/Ti) for catalytic PET polycondensation

PET (poly(ethylene terephthalate)) is one of the most important type of thermoplastic polyesters and widely used in various fields. Titanium-based catalysts are environmentally friendly and have higher catalytic activity than antimony-based catalysts when used in industry. However, titanium-based catalysts are prone to hydrolysis and result in discolored products. UiO-66 (Zr/Ti) with different Ti4+ contents were successfully synthesized via one-step method. The material was characterized by XRD, SEM, FT-IR, XPS, BET and TG techniques. The results demonstrates that Ti4+ was integrated into the UiO-66 framework. NH3-in situ DRIFTS, pyridine-IR, and NH3-TPD were used to explore the acidic properties of the samples, which proved that stable Lewis acidic sites are present in the samples even at 300 °C. The catalytic performance of UiO-66 (Zr/Ti) containing different Ti4+ was explored under different conditions. At the same time, the scale-up experiment was carried out in a 5 L reactor, and the PET chips obtained had a lower b value. The catalytic reaction mechanism of UiO-66(Zr/Ti) was demonstrated by DFT calculations and the catalytic performance was close to Sb-based catalysts.

Potential of Functionalized Polyolefins in a Sustainable Polymer Economy: Synthetic Strategies and Applications.

Polymers play a crucial role in our modern life as no other material exists that is so versatile, moldable, and lightweight. Consequently, the demand for polymers will continue to grow with the human population, modernization, and technological developments. However, depleted fossil resources, increasing plastic waste production, ocean pollution, and related growing emission of greenhouse gases has led to a change in the way we think about the use of polymers. Although polymers were never designed to be recycled, it is clear that a linear polymers economy is no longer sustainable. The design for recycling and reuse and life-cycle analyses will become increasingly important factors when deciding on which polymer to choose for a certain application. Of all polymers, polyolefins have the lowest life-cycle environmental impact and even outperform renewable polymers. However, polyolefins are chemically inert and reveal a low surface energy. Combining their excellent mechanical properties with the ability to adhere to other materials or create self-assembled or nanostructured materials would widen the application window of polyolefins even more.This Account covers part of our personal account in the field of functionalized polyolefin synthesis and their application development. We start with addressing the challenge of finding suitable catalysts that tolerate nucleophilic functionalities, which tends to poison most electrophilic catalysts even when passivated with, for example, an aluminum alkyl. We argued that lowering of the oxidation state of a titanium-based catalyst might lower the electrophilicity of the metal center. Indeed, this simple approach resulted in an unprecedentedly high tolerance toward aluminum alkyl-passivated alkenols during their copolymerization with ethylene. Interestingly, catalyst deactivation was much less pronounced during the copolymerization of propylene and aluminum-passivated alkenols, clearly demonstrating the protective effect of the methyl branch in the growing polymer. Because the use of randomly functionalized polypropylenes is rather underdeveloped, as compared to the corresponding randomly functionalized polyethylenes, we focused on potential applications of the former material. Atactic or low-crystalline hydroxyl- and carboxylic acid-functionalized propylene-based co- and terpolymers form elastomers with interesting properties that can be influenced by enhancing the hydrogen bonding within the system or by creating ionomers. The polar functionalities cluster together in domains that can host small polar molecules such as, for example, a pH indicator, thus affording useful sensors. The functionalized polyolefins can also be used as precursors for amphiphilic graft copolymers, undergoing self-assembly and therefore being suitable for nanoporous membrane preparation. The graft copolymers also proved to be effective compatibilizers in various polymer blends.

Ethylene glycol-soluble Ti/Mg-citrate complex catalyst for synthesis of high intrinsic viscosity poly(ethylene terephthalate)

Antimony-free poly(ethylene terephthalate) (PET) has been synthesized through polycondensation of p-phthalic acid and ethylene glycol, and then subjected to a viscosity-increasing process by liquid-state polycondensation (LSP). For both of these processes, a novel environmentally benign ethylene glycol-soluble Ti/Mg bimetal (TM) catalyst has been used. The structure of the TM catalyst has been comprehensively characterized and its catalytic activity in the polycondensation reaction has been evaluated and compared with those of other titanium-based catalysts. The results reveal that the TM catalyst is a chelated complex with high catalytic activity for polycondensation to afford PET without significant side reactions. Indeed, the LSP process catalyzed by TM affords a PET product with high intrinsic viscosity suitable for industrial yarn production (1.08 dL/g) within 60 min, and that exhibits higher thermostability with increasing intrinsic viscosity. Finally, the kinetics of the TM-catalyzed polycondensation has been probed based on the variation of intrinsic viscosity with increasing polycondensation time.

Kinetic studies on Lewis acidic metal polyesterification catalysts - hydrolytic degradation is a key factor for catalytic performance.

Kinetic analysis of polyesterification reactions using Lewis-acidic metal catalysts have been performed. While Sn-based catalysts are superior to Ti-based catalysts under neat polycondensation conditions (high [H2O]), the result is inverted under azeotropic conditions (low [H2O]). These findings show that the catalytic activity is crucially determined by the robustness of the catalyst against hydrolytic degradation.

MIL-53(Al) catalytic synthesis of poly(ethylene terephthalate).

Poly(ethylene terephthalate) (PET) is one of the world's five major engineering plastics and is widely used in various fields. At present, the main catalysts used in the synthesis of PET are antimony, titanium, and aluminum metal compounds. Among them, antimony-based catalysts are poisonous and the titanium-based catalyst products are relatively yellow in hue. The aluminum-based catalyst has the advantages of low price and environmental friendliness, but current research shows that the organoaluminum catalyst has the problem of hydrolysis, and MIL-53 (Al) has good stability and will not affect the environment, so we add a catalyst before the esterification reaction, and uses thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscope (SEM), and N2 low-temperature physical adsorption characterizes the thermal stability and structure of MIL-53(Al). At the same time, the effects of different content, polycondensation time, before and after activation and polycondensation temperature on the properties of PET were investigated. The research results show that when the molar content of catalyst is 0.05% and the reaction temperature is 280 °C for 150 min, the product obtained is relatively excellent. The catalytic activity has almost no effect before and after activation, indicating that the polycondensation reaction is carried out on the surface of the catalyst. Therefore, MIL-53 (Al) has great potential in PET industrial catalysis.

Synthesis and characterisation of polyamides based on 2,5-furandicarboxylic acid as a sustainable building block for engineering plastics

This paper reports the synthesis of high molecular weight semi-aromatic polyamides containing renewable furanic monomer by a scalable melt polycondensation method using eco-friendly titanium-based catalysts.

Effect of different introduction methods of cerium and tin on the properties of titanium-based catalysts for the selective catalytic reduction of NO by NH3

This work investigated the influence of introduction methods of cerium and tin on the physicochemical properties as well as the activity and durability of titanium-based catalysts for the selective catalytic reduction of NO by NH3 (NH3-SCR). Precipitation and impregnation methods were adopted to synthesize a series of cerium-tin-titanium catalysts. These catalysts were characterized by XRD, Raman, N2 adsorption–desorption, HRTEM, EDS mapping, XPS, H2-TPR, NH3-TPD and in situ DRIFT. Notably, Ce/Sn/Ti(imp) catalyst prepared by stepwise-impregnation method could provide an interface between Ce and Sn for more facile electron transfer than Sn/Ce-Ti(co), Ce/Sn-Ti(co) and Sn/Ce/Ti(imp) catalysts. It promoted the redox equilibrium of Ce4+ + Sn2+ ↔ Ce3+ + Sn4+ shifting to right to produce adequate Ce3+ and surface adsorbed oxygen, resulting in optimal reducibility and surface acidity of Ce/Sn/Ti(imp) catalyst. Besides, the activation of NH3 and desorption of NOx readily occurred on the surface of Ce/Sn/Ti(imp), which were favorable for the proceeding of subsequent reactions and excellent performance of NH3-SCR.

Solar-active titanium-based oxide photocatalysts loaded on TiN array absorbers for enhanced broadband photocurrent generation

Efficient utilization of a wide range of the solar spectrum in photoelectrochemical conversion is one of the primary requirements for photocatalyst materials. Here, we report an effective approach to combine solar-absorptive titanate-based oxide photocatalysts with titanium nitride (TiN) to demonstrate the enhanced photocurrent generation extending from the ultraviolet to the near-infrared region. Pseudobrookite Fe2TiO5 and Cr-doped TiO2 are, respectively, loaded on the TiN nanodisk arrays to demonstrate the photocurrent generation in opposite directions. By incorporating the TiN nanodisk arrays, the photocatalytic performance of Fe2TiO5 has increased by 26-fold in the UV region and ∼11-fold in the visible region due to the strong UV–visible light absorption, hot electron generation at the TiN nanodisk array, and their subsequent injection into the oxide. Similarly, the photocatalytic performance of Cr-TiO2 has increased by ∼18-fold in the UV region and ∼sixfold in the visible region by the hot hole transfer from TiN. This work demonstrates the effective utilization of titanium-based catalysts activated with both hot-electrons and holes from the TiN, yielding the visible-photocurrent generation and thus the improved photon management in solar photocatalysis.